Salts of certain methylene diamines with certain petroleum sulphonic acids



Patented Mar. 21, 1944 reasse- SALTS OF CERTAIN METHYLENE DIAMINES -WITHCERTAIN PETROLEUM SULPHONIC ACIDS Melvin De Groote, University City,Mo., assignor, by mesne assignments, to Petrolite Corporation, Ltd., acorporation of Delaware No Drawing. Original application May 12, 1939,

Serial No. 273,221. =Divided and this application June 1'7, 1941, SerialNo. 398,494

3 Claims.

This invention relates to a new composition of matter consisting of acertain kind of amine salt derived from water-soluble petroleumsulphonic acid or acids of the kind hereinafter described.

This application is a division of my prior application Serial No.273,221, filed May 12, 1939.

The main object of my invention is to provide a new material orcomposition of matter that is an eflicient solubilizer, particularly ininstances where it is desired to make two immiscible materials mutuallysoluble, and which is also capable of use as a demulsifier for crude oilemulsions, either alone, or in admixture with conventional demulsifyingagents, such for example, as demulsifying agents of the modified fattyacid type, or of the alkylated aromatic sulphonic' acid type.

Petroleum sulphonic acids are produced from a wide variety of petroleumdistillates or petroleum fractions, and in some instances, they areproduced from the crude petroleum itself. When produced from crudepetroleum itself, it is customary to use crude oil of the naphthenetype, crude oil of the paramn type, crude oil of the asphaltic type andmixtures of said three different types of crude oil.

The art of refining petroleum crude or various fractions, usingsulphuric acid of various strengths, as well as monohydrate and fumingacid, is well knownprocedure. In such conventional refining procedure,petroleum sulphonic acids have been produced as icy-products. Forinstance, in removing the olefinic components, it has been commonpractice to use sulphuric acid so as to polymerize the olefines orconvert them into sulphonic acids which are subsequently removed.Likewise, in the production of white oil or highly refined lubricatingoils,'it has been customary to treat with fuming sulphuric acid, so asto eliminate certain undesirable components.

In recent years, certain mineral oil fractions have been treated withsulphuric acid with the primary object of producing petroleum sulphonicacids. and in such procedure the petroleum sulphonic acids representedthe primary objects of reaction, rather than concomitant lay-products.Petroleum sulphonic acid, regardless of whether derived as the principalproduct of reaction or as a by-product, can be divided into two generaltypes, to wit, green acid or acids and mahogany acid or acids. The greenacids are characterized by being water-soluble or dispersible. In otherwords, they form either true solutions or sols.

referred to as water-soluble without any effort to indicate whether thesolution is molecular or colloidal in nature. The green acids, asindicated by their name, frequently give an aqueous solution having adark green or grey-green appearance. They generally appear as acomponent of the acid draw-off and do not remain behind dissolved in theoil fraction which has been subjected to sulphuric acid treatment. Thegreen acids are not soluble in oil, even when substantially anhydrous,and certainly are not soluble in oil when they contain as much as 15% ofwater. Similarly, their salts obtained by neutralization with a strongsolution of caustic soda, caustic potash, or ammonia, are notoil-soluble. For convenience of classification, the ammonium salt willbe considered as an alkali salt.

In contradistinction to the hydrophile green acids, there occurs, as inthe manufacture of medicinal white oil, the oil-soluble type or themahogany acids. These mahogany acids are characterized by being solublein oil, especially when anhydrous, and being soluble in oil, even ifthey contain some dissolved water. Some of the mahogany acids also showlimited hydrophilic properties to the extent that either some water canbe dissolved in the acids, or they, in turn, may dissolved to someextent in water. In some instances their salts, such as the sodium,ammonium, or potassium salt, will dissolve in water to give a colloidalsol. However, regardless of the presence of any hydrophilic propertieswhatsoever, they always have a charactertistic hydrophobe property, asindicated by the fact that the substantially anhydrous form, forinstance, their alkali salts containing 5-12% water,

' will dissolve in oil. i This clearly distinguishes them from the greenacids previously referred to, because the green acids in similar formcontaining the same amount of water, for example,

will not dissolve in oil. The green acids, as such,

For purpose of convenience, they will be herein as are essentiallyhydrophilic and non-hydrophobic in character.

The utility of the mahogany acids in various arts has been enhanced byincreasing their water solubility; for instance, converting the mahoganyacids into hydroxy alkylamine salts. On the other hand, as far as I amaware, no valuable product of commerce has resulted from decreasing thewater solubility of the mahogany acids by the addition of someoil-soluble basic amine, such, for example, as triamylamine. Thetriamylamine salts of mahogany acids for example, are completely devoidof any solubility in water which the alkali salts may have exhibited andshow, as

would be expected an increased solubility in hydrophobe solvents.

Green acids are hydrophile in character, as previously stated. Theirhydrophile character has been increased by neutralization with materialssuch as triethanolamine and the like. Such green acid salts havingenhanced water solubility, as compared with the ordinary alkali salts,have found application in certain arts.

I have found that when green acids, i. e., the oil-insoluble type, areneutralized with a diamine of the kind hereinafter described, so as toproduce a water-insoluble product, that the resulting material, eventhough it does not exhibit any marked oil solubility, especially when itcontains 5-10% of water, still has pronounced valueas a demulsifier foroil field emulsions, either when used alone, or in conjunction withother known demulsifying agents. I employ diamines of the kind derivablemost readily by reactions involving an aldehyde and a secondary amine,all of which is hereinafter described in detail. I have also found thatsometimes such amine salt of green acids will mix in with a hydrophobematerial and a hydrophile material, so as to produce a homogeneousmixture. The effectiveness of the above described material orcomposition of matter as a demulsifying agent for oil field emulsionsappears to be related to some factor other than its solubilitycharacteristics.

The new composition of matter which constitutes my present invention isrepresented by amine salts of hydrophilic non-hydrophobic greenpetroleum acids, as exemplified by the salt derived from such greenacids by neutralization with the diamine obtained by reaction betweentwo moles of diamylamine and one mole of formaldehyde or one mole ofacetaldehyde. The manufacture of said composition of matter involvesnothing more or less than neutralizing one mole of the selectedpetroleum acid with a mole of a suitable amine, or neutralizing twomoles of the selected petroleum sulphonic acid with one mole of theamine, in that the amine being a diamine, is dibasic. In the lattercase, a suitable indicator, such as methyl orange indicator, may beemployed. For purposes of convenience, I prefer that the selectedpetroleum sulphonic acid contain not over 15% of water. It isunderstood, of course, that the conventional procedure, employing doubledecomposition instead of direct neutralization, can be utilized in themanufacture of my new material or composition of matter. For instance,the sodium salt of the selected petroleum sulphonic acid can bedissolved in alcohol or other suitablesolvent, and the aminehydrochloride added so that sodium chloride will precipitate. Afterfiltering off the precipitated sodium chloride, the alcohol can beevaporated and the amine salt recovered. If desired, a mix ture ofamines instead of a single amine may be employed.

It is well known that certain monocarboxy organic acids, containingapproximately eight carbon atoms or more, and not more than thirtytwocarbon atoms, are characterized by the fact that they combine withalkalies to produce soap or soap-like materials. These detergent-formingacids include fatty acids, resin acids, petroleum acids, etc. For thesake of convenience, these acids will be indicated by the formulaR.COOH.

It is also well known that diamines, having pronounced basic properties,may be derived by various means, provided that the resultant diamine ischaracterized by the fact that the two amino nitrogen atoms are notattached to the same carbon atom. Such diamines, generally referred toas alkylene diamines, are well known and may be characterized byethylene diamine. Derivatives of the diamines herein contemplated arecharacterized by being a methylene diamine derivative, 1. e., aderivative of the hypothetical methylene diamine ondary amines areavailable, which may be designated by the formula type:

in which B represents an alkyl, aralkyl, alicyclic, alkylol, aralkylol,hydroxy alicyclic, heterocyclic, or other equivalent radical. B and Bjointly may represent one radical, as in piperidine.

It is well known that aldehydes, particularly the aldehydes ofrelatively low molecular weight,

such as formaldehyde, acetaldehyde, aldol, furfural, benzaldehyde,hexahydro-benzaldehyde, phenyl-acetaldehyde, etc., can combine with twomoles of a secondary amine, so as to yield a methylene diamine,characterized by the fact that the two amino nitrogen atoms are attachedto the same carbon radical. Such reaction may be indicated in thefollowing manner:

The amine so produced may be indicated by the following formula:

in which, as has been previously pointed out, T may represent a hydrogenatom derived from formaldehyde, or may represent a radical derived fromacetaldhyde, propionaldehyde, butyraldehyde, heptaldehyde, lauricaldehyde, palmitic aldehyde, or stearic aldehyde.

Similarly, instead of aliphatic aldehydes, one may employ heterocyclicaldehydes, such as furfuraldehyde, or aromatic aldehydes, such asbenzaldehyde. Unsaturated aldehydes, such as acrolein, crotonaldehyde,tiglic aldehydes, may be employed. As previously indicated, Brepresentsa radical, such as the methyl, ethyl, propyl, butyl, amyl, hexyl, octyl,decyl, hexadecyl, octadecyl, or a similar radical. Similarly, B mayrepresent an. aralkyl radical, such as a benzyl radical, ethyl benzylradical, dimethyl benzyl radical, an alicyclic radical, such as thecyclohexyl, methyl cyclohexyl, etc.; likewise, B may represent a hydroxyethyl, hydroxy propyl, hydroxy butyl, and similar radicals, such as aCeH4C2H4OH radical, or a CsHmOI-I radical; Other radicals include thefurfural radical, or hydroxy derivatives thereof. Piperidine may beconsidered as a special adaptation in which one radical replaces twoamino hydrogen atoms.

It is to be noted that the methylene diamine, expressed by the aboveformula, is a tertiary diamine in the sense that neither amino nitrogenatom has attached thereto a replaceable hydrogen atom. For convenience,the above formula may be rewritten as follows, so as to indicate suchinstances where there is present an alcoholic hydroxyl radical:

in which B OH is obviously the monovalent hydroxy hydrocarbon radical,such as an alkylol radical or the like. Needless to say, B'OH may occurmore than once, and B may occur less than three times. It is well knownthat amines such as triethanolamine or the like can be acylated byreaction with fatty acids or a suitable functional derivative thereof,such as the acyl chloride or the anhydride, or even the ester. If thetertiary hydroxy methylene diamine of the kind just described is reactedwith a detergent-forming monobasiccarboxy acid, the reaction may beindicated in the following manner:

with the formation of an intermediate ester which may be indicated inthe following manner:

In addition to aldol, other similar hydroxy aldehydes oraldehyde-alcohols may be employed. As to such aldehydes other thanaldol, reference is made to Richters Organic Chemistry, volume 1, thirdEnglish edition, 1934, pages 389-391.

In view of what has been said previously, it does not appear necessaryto enumerate various suitable amines which may be employed, but it maybe well to indicate that among those which may be employed are thefollowing: diethanole amine, dipropanolamine, dibutanolamine,dipentanolamine, dioctanolamine, glyceryl dihexanolamine, methylglycerylamine, ethyl glycerylamine, propyl glycerylamine, cyclohexylglyceryltil amine, benzyl glycerylamine; dibenzylamine, ethylbenzylamine, methyl benzylamine, propyl benzylamine, cyclohexylethylamine, cyclohexyl propylamine, cyclohexyl hexylamine, diethylamine,dipropylamine, diamylamine, dihexylamine, dioctylamine, diglycerylamine,etc. In all the previous examples, each radical indicates a substituentfor an amino hydrogen atom. Similarly, amines can be obtained frompolyglycerols or polyglycols, as for instance, the secondary amines,indicated by the following formulas:

Such amines may serve as functional equivalents of the previouslydescribed amines, which happen to be free from an ether linkage.Likewise, one may have amines in which there is more than one etherlinkage, i. e., in which the hydrocarbon radical, which replaces anamino hydrogen atom, has been interrupted more than once by an oxygenatom.

In examining the previous formulas, it becomes evident that if twodifferent amines are employed the reaction is not limited to the twodissimilar amines, but may take place in part in such a manner as toinvolve two similar amines. In other Words, if the two different aminesbe indicated as A and B, the reaction is not limited to the diamineinvolving both A and B, but in part the diamine will be formed solelyfrom two molecules of A, and in part solely from two molecules of B. Forpractical purposes, then, it is most expedient, in the majority ofinstances, to manufacture or produce a methylene diamine from a singlekind of secondary amine; and in such event, everything else being equal,it is most desirable to use the cheapest secondary amine available thatwill produce at least a fairly waterinsoluble product, and the cheapestaldehyde available. I particularly prefer to use diethanolamine and tocompletely or at least partially esterify the diethanolamine with a longchain carbon atom acid, particularly a detergent-forming acid, having atleast 8 carbon atoms and not more than 32 carbon atoms, such as oleicacid, naphthenic acid, or abietic acid. Naturally the introduction ofone or more of such long chain carbon compounds greatly increases theoil solubility of the amine; and such oil solubility is transposed, atleast in part, to the final product, which is a salt of the sulphonicacid. As previously pointed out, it is not believed that oil solubilityper se is the index as to effectiveness of the demuisifying agent. Onemay, of course, employ the hydroxylated diamine Without acylation, butin such event, my experience has been that it is more preferable perhapsto employ diamylamine. Similarly, attention is again directed to thefact that wherever hydroxyl radicals exist, then such hydroxyl radicalmight be reacted with an acid having less than 8 carbon atoms, forinstance, acetic acid, butyric acid, heptoic acid, etc. More than onehydroxy hydrocarbon radical, if present, may be acylated, and if two ormore such radicals are reacted with acids, one need not employ the sameacids, but different acids may be employed. A hydroxy radical attachedto the aldehyde residue may be similarly acylated, as, for example, theresidue from aldol. A compound, such as sodium hydrogen phthalate, mightbe used for acylation.

My preferred reagent is manufactured in the following manner:

Two moles of diamylamine are cautiously reacted with a solution offormaldehyde, or preferably, with acetaldehyde, with cooling during theearly stages to prevent the reaction from taking place too rapidly, andwith a slight application of heat during the latter stages, so as toobtain complete reaction,

The methylene diamine so obtained may be indicated by the followingformula:

C511 CH3.C

If desired, of course, the product obtained by reaction can be purifiedin the customary manner, so as to remove any unreacted aldehyde, andalso any unreacted simple secondary amine. However, if the reaction isconducted carefully, a substantial and generous yield of the desiredcliamine is obtained, and it is unnecessary to resort to anypurification. It has been previously pointed out that having obtained anamine of the kind desired, it is only necessary to proceed to neutralizethe green acid, as previously indicated.

Incidentally, it may be well to point out that one particularlydesirable mixture of diamines is obtained by employing one mole ofdiethanolamine and one mole of diamylamine in connection with one moleof acetaldehyde. ant product so obtained will average two hydroxylradicals per molecule; and one hydroxyl radical can be readilyeliminated by acylation with one mole of a selected acid, particularlyoleic acid or naphthenic acid. If desired, both hydroxyl radicals may beeliminated. In this instance the long carbon chain attached to an aminonitrogen atom is interrupted by an oxygen atom. It is understood in thehereto appended claims that reference to a hydrocarbon radical includessuch radicals that are essentially hydrocarbon in nature, which includecarbon atom chains that are interrupted at least once by an oxygen atom.This would occur, of course, in linkages such as the following:

Ncinioon where R is the hydrocarbon radical derived from naphthenicacid, oleic acid, acetic acid, heptoic acid, or the like. Acylation canbe accomplished by any suitable acid compound, such as the acylchloride, the anhydride, etc. If an amine salt is formed, such as thehydrochloride, it must be converted into a base by conventionaltreatment with strong caustic soda or the like.

Returning momentarily to the preparation of the preferred reagent, noadditional information is required. However, it may be well to point outthat I prefer to use a green acid selected so The resultthat it isrelatively free from inorganic acid, such as sulphurous acid andsulphuric acid, and containing not over 15% water, and preferably, aslittle unsulphonated hydrocarbon material as possible. A convenientamount of such material, for instance, a thousand pounds, is neutralizedwith a diamyl diamine previously described, so that the resultantcompound indicates neutral or slightly basic to methyl orange, or someother acceptable indicator.

It may be well to point out that hydrophile non-hydrophobe petroleumsulphonic acid or acids of the green acid type vary somewhat; forinstance, the molecular weight may vary within the range of 350-500 orthereabouts. Naturally, these petroleum sulphonic acids may carry somepolymerized olefins, free hydrocarbons, or the like or may even carry abit of naphthenic acids which represent carboxylated non-sulphonatedpetroleum acids. As previousl stated, these materials are well knowncommercial products, and are available in the open market, either in theform of the acid itself, or in the form of a salt.

In the claims the amine or, more specifically, the diamine, is referredto asbasic to indicate that the basicity is in the neighborhood of thatof ammonia, triethanolamine, or amylamine. In some instances thebasicity may be somewhat greater, in fact, perhaps considerably greater,and in some instances perhaps slightly less. In order to insure suchbasicity, it is necessar that there be no aryl or aromatic radicalattached to the amino nitrogen atom from which the diamine is produced.In other words, such material as phenyl amylamine, diphenylamine, phenyloctylamine, etc., are not satisfactory, due to the presence of thearomatic phenyl radical or an aryl radical, such as the naphthyl radicalattached directly to the amino nitrogen atom. In the event that sucharyl radical is attached to the amino nitrogen atom, the basicity of theamine is reduced to that of the aniline, or the like. Such amines of lowbasicity do not form stable salts with the petroleum acids of the kinddescribed. For this reason the expression basic is employed to clearlycharacterize the amine. The term sulphonic acid used in the claims isintended to refer to a substance consisting either of a single acid or amixture of acids.

In my divisional application Serial No. 300,843, filed October 23, 1939,I have described a novel process for resolving or breaking petroleumemulsions of the water-in-oil type. Said process involves subjecting theemulsion to the action of a demulsifier consisting of the abovedescribed new material or composition of matter. Said material is usedeither alone or in admixture with another or with other conventionaldemulsifying agents, and its method of use is the same as that generallyemployed in resolving or breaking petroleum emulsions of thewater-in-oil type with a chemical demulsifier. Briefly stated, theconventional method of using a chemical demulsifier to break a petroleumemulsion consists in introducing the demulsifier into the well in whichthe emulsion is produced; introducing the demulsifier into a conduitthrough which the emulsion is flowing; or introducing the demulsifierinto a tank in which the emulsion is stored. After treatment theemulsion is allowed to stand in a quiescent state, usually in a settlingtank, and usually at a temperature varying from atmospheric temperatureto about 200 F., so as to permit the water or brine to separate from theoil, it being preferable to keep the temperature low enough to preventth volatilization of valuable constituents of the oil. The amount ofdemulsifier that may be required to break the emulsion may vary from 1part of demulsifier to 500 parts of emulsion, up to 1 part ofdemulsifier to 20,000 or even 30,000 parts of emulsion.

I desire to point out that the superiority of the reagent ordemulsifying agent herein described is based upon its ability to treatcertain emulsions more advantageously and at a somewhat lower cost thanis possible with other available demulsifiers, or conventional mixturesthereof. It is believed that the particular demulsifying agent ortreating agent herein described will find comparatively limitedapplication, so far as the majority of oil field emulsions areconcerned; but I have found that such a demulsifying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in a number of cases which cannot be treated as easily or atso low a cost with the demulsifying agents heretofore available.

I claim:

1. A new compound consisting of a waterinsoluble salt of a basic,methylene diamine of the formula type:

in which T is selected from the class consisting of hydrogen atoms,hydroxy alkyl radicals and aliphatic hydrocarbon radicals and B isselected from the class consisting of aliphatically-bound hydrocarbonradicals, alicyclic hydrocarbon radicals, aliphatic hydrocarbon radicalsinterrupted at least once by an oxygen atom, aliphatically-bound hydroxyhydrocarbon radicals, hydroxy alicyclic radicals, and radicals obtainedby the acylation of a hydroxy hydrocarbon radical in which the acylatingcompound is derived from an acid containing not more than 32 carbonatoms, at least one of the radicals represented by B being such anacylated hydroxy hydrocarbon radical; said diamine salt being obtainedfrom water-soluble, non-hydro-phobe petroleum sulphonic acid of thegreen acid type.

2. A new compound consisting of a water-insoluble salt of a basic,methylene diamine of the formula type:

in which E is selected from the class consisting of aliphatically-boundhydrocarbon radicals, alicyclic hydrocarbon radicals, aliphatichydrocarbon radicals interrupted at least once by an oxygen atom,aliphatically-bound hydroxy hydrocarbon radicals, hydroxy alicyclicradicals, and radicals obtained by the acylation of a hydroxyhydrocarbon radical in which the acylating compound is derived from anacid containing not more than 32 carbon atoms, at least one of I theradicals represented by B being such an acylated hydroxy hydrocarbonradical; said diamine salt being obtained from water-soluble,non-hydrophobe petroleum sulphonic acid of the green acid type.

3. A new compound consisting of a water-insoluble salt of a basic,methylene diamine of the formula type:

H/ \NB in which T is a hydroxy hydrocarbon radical and B is selectedfrom the class consisting of aliphatically-bound hydrocarbon radicals,alicyclic MELVIN DE GROOTE.

